JP5636456B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition that is a precursor of a heat resistant resin used as a surface protective film or an interlayer insulating film of a semiconductor device, and a heat-resistant curing using the positive photosensitive resin composition. The present invention relates to a method for manufacturing a relief pattern and a semiconductor device having the cured relief pattern.

  Polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like are widely used for surface protection films and interlayer insulating films of semiconductor devices. This polyimide resin is currently often provided in the form of a photosensitive polyimide precursor composition. In the process of manufacturing a semiconductor device, the precursor composition is applied to a substrate such as a silicon wafer, patterned with actinic rays, developed, and subjected to a thermal imidization treatment to become a part of the semiconductor device. A surface protective film, an interlayer insulating film, or the like can be easily formed. Therefore, the manufacturing process of a semiconductor device using a photosensitive polyimide precursor composition is a manufacturing process using a conventional non-photosensitive polyimide precursor composition that needs to be patterned by a lithography method after forming a surface protective film or the like. Compared with the process, it has the feature that the process can be greatly shortened.

By the way, this photosensitive polyimide precursor composition requires the use of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the development process. Countermeasures are being sought. In response to this, recently, various proposals have been made on heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution, as with photoresists.
Among them, a PBO precursor composition in which an alkaline aqueous solution-soluble hydroxypolyamide, such as polybenzoxazole (hereinafter, also referred to as “PBO”) precursor, which becomes a heat-resistant resin after curing, is mixed with a photoacid generator such as a naphthoquinonediazide compound. The method of using a product as a positive photosensitive resin composition is disclosed in the following Patent Document 1 and Patent Document 2, and has attracted attention in recent years.
The development mechanism of this positive photosensitive resin composition is that the naphthoquinone diazide compound and PBO precursor in the unexposed area have a low dissolution rate in an alkaline aqueous solution, whereas the photosensitive diazoquinone compound is converted to indenecarboxylic acid by exposure. This is based on the fact that the dissolution rate of the exposed portion in the alkaline aqueous solution is increased by chemical change to the compound. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern composed of the unexposed portion can be created.

  The PBO precursor composition described above can form a positive relief pattern by exposure and development with an alkaline aqueous solution. Further, heat generates an oxazole ring, and the cured PBO film has the same thermosetting film characteristics as a polyimide film. Therefore, the PBO precursor composition is a promising organic solvent development type polyimide precursor composition. Has attracted attention as an alternative material.

Japanese Examined Patent Publication No. 01-046862 JP 63-096162 A JP 2002-12761 A JP 2005-134743 A

  However, the PBO precursor composition has a lower sensitivity than the photosensitive polyimide precursor composition due to the problem associated with the absorption wavelength of the photosensitive agent, and therefore there is a demand for a more sensitive composition. In addition, since these cured films are used for surface protective films and the like, they require good thermal and mechanical properties and good adhesion to a substrate such as Si as a base.

Patent Document 3 discloses a heat resistant resin composition containing a compound having a triazine skeleton and / or a vinyl group and a PBO precursor resin as essential components. In addition, a curable organic compound having two or more unsaturated groups and / or epoxy groups together with at least one imide group in the molecule, and a resin binder having a carbonyl group bonded to a hetero atom in the main chain are bisallylnaphthal. A method for improving sensitivity and thermomechanical characteristics by using a diimide compound or a bismaleimide compound has been proposed (Patent Document 4), but if the polymer structure does not have an imide group, the function as a resist is manifested. Therefore, it is assumed that the developing mechanism is fundamentally different and the effect of improving the sensitivity is not sufficient. Moreover, since the resin used as the binder does not undergo cyclization change unlike the PBO precursor, there is no change in Tg and it is considered that there is almost no influence on the cured shape.
The problem to be solved by the present invention is a positive photosensitive resin composition having a positive lithography performance with excellent pattern shape after curing of the resin, high sensitivity and high adhesion, and curing using the composition A relief pattern manufacturing method and a semiconductor device having the cured relief pattern are provided.

  The present inventor has found that a photosensitive resin composition that solves the above problems can be obtained by combining a specific compound with a heat-resistant alkaline aqueous solution-soluble polymer having a specific structure, and has led to the present invention. It was.

｛式中、Ｘ_１は、少なくとも２個の炭素原子を有する４価の有機基であり、Ｙ_１は、少なくとも２個の炭素原子を有する２価の有機基であり、そしてｍ_１は、１〜１０００の整数である。｝で表されるヒドロキシアミド構造を有するアルカリ水溶液可溶性重合体１００質量部に対して、（Ｂ）光酸発生剤１〜５０質量部、（Ｃ）下記一般式（２）：

｛式中、Ｄ_１は、水素原子、炭素数１〜６のアルキル基、アルケニル基、及び架橋し得る有機基からなる群より選ばれる官能基を少なくとも１つ有し、Ｍ_１は、−ＣＨ_２−、−Ｏ−、及び−Ｓ−からなる群から選択される基を示し、Ｚ_１は、２価の有機基であり、ｎ_１は、０〜４の整数であり、そしてＤ_１が複数ある場合、複数のＤ_１は同じでも異なっていてもよい。｝で表される化合物１〜４０質量部を含むことを特徴とする感光性樹脂組成物。 That is, the present invention is as follows.
[1] (A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, Y ₁ is a divalent organic group having at least 2 carbon atoms, and m ₁ is 1 It is an integer of ~ 1000. } With respect to 100 parts by mass of the aqueous alkali-soluble polymer having a hydroxyamide structure represented by (B), 1 to 50 parts by mass of a photoacid generator, (C) the following general formula (2):

{In the formula, D ₁ has at least one functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an organic group that can be cross-linked, and M ₁ represents —CH ₂ represents a group selected from the group consisting of —O— and —S—, Z ₁ is a divalent organic group, n ₁ is an integer of 0 to 4, and D ₁ is When there are a plurality, D ₁ may be the same or different. } The photosensitive resin composition characterized by including 1-40 mass parts of compounds represented by this.

  [2] The photosensitive resin composition according to the above [1], wherein the (B) photoacid generator is a compound having a naphthoquinonediazide structure.

で表される化合物からなる群から選択される、前記［１］又は［２］に記載の感光性樹脂組成物。 [3] (C) The compound represented by the general formula (2) is represented by the following general formula (3):

The photosensitive resin composition as described in said [1] or [2] selected from the group which consists of a compound represented by these.

｛式中、Ｘ_３は、単結合及び下記一般式（５）：

で表される構造からなる群より選ばれる少なくとも一種の構造を示し、Ｌ_１、Ｌ_２、及びＬ_３は、各々独立に、水素原子又はメチル基を示し、そしてＬ_４は、水素原子、メチル基又は水酸基を表す。｝で表される構造を有する、前記［１］〜［３］のいずれかに記載の感光性樹脂組成物。 [4] (A) An aqueous alkaline solution-soluble polymer having a hydroxyamide structure represented by the general formula (1) is represented by the following general formula (4):

{In the formula, X ₃ represents a single bond and the following general formula (5):

And L ₁ , L ₂ , and L ₃ each independently represent a hydrogen atom or a methyl group, and L ₄ represents a hydrogen atom, a methyl group, or a methyl group. Represents a group or a hydroxyl group. } The photosensitive resin composition in any one of said [1]-[3] which has a structure represented by these.

｛式中、Ｌ_５は−ＣＨ_２−、−Ｏ−、及び−Ｓ−からなる群から選択される基を示し、そしてＬ_６は、水素原子又はアルキル基を示す。｝からなる群から選択される、前記［１］〜［４］のいずれかに記載の感光性樹脂組成物。 [5] (A) The terminal of the aqueous alkaline solution-soluble polymer having a hydroxyamide structure represented by the general formula (1) is represented by the following general formula (6):

{Wherein L ₅ represents a group selected from the group consisting of —CH ₂ —, —O—, and —S—, and L ₆ represents a hydrogen atom or an alkyl group. } The photosensitive resin composition according to any one of [1] to [4], selected from the group consisting of:

  [6] (1) Step of forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] on a substrate, (2) Exposure with actinic radiation through a mask Or a step of directly irradiating a light beam, an electron beam or an ion beam, (3) a step of eluting or removing the exposed portion or the irradiated portion, and (4) a step of heat-treating the obtained relief pattern. And a method for producing a cured relief pattern.

  [7] A semiconductor device having a cured relief pattern obtained by the method according to [6].

  According to the present invention, a positive photosensitive resin composition having a positive lithography performance with excellent pattern shape at the time of curing of the resin, high sensitivity and high adhesion, and curing using the positive photosensitive resin composition A method for producing a relief pattern and a semiconductor device having the cured relief pattern are provided.

FIG. 1 shows a cross section of a 50 μm line of a post-cure relief pattern, which was observed using an S-2400 type Hitachi scanning electron microscope manufactured by Hitachi, Ltd.

｛式中、Ｘ_１は、少なくとも２個の炭素原子を有する４価の有機基であり、Ｙ_１は、少なくとも２個の炭素原子を有する２価の有機基であり、そしてｍ_１は、１〜１０００の整数である。｝

｛式中、Ｘ_１は、少なくとも２個以上の炭素原子を有する４価の有機基であり、Ｘ_２、Ｙ_１、及びＹ_２は、それぞれ独立に、少なくとも２個以上の炭素原子を有する２価の有機基であり、ｍ_１は、１〜１０００の整数であり、ｍ_２は、１〜５００の整数であり、ｍ_１／（ｍ_１＋ｍ_２）＞０．５であり、Ｘ_１及びＹ_１を含むｍ_１個の単位、並びにＸ_２及びＹ_２を含むｍ_２個の単位の配列順序は問わない。｝ <Photosensitive resin composition>
Each component constituting the photosensitive resin composition will be specifically described below.
(A) Alkaline aqueous solution-soluble polymer In the case of an alkaline aqueous solution-soluble polymer having a hydroxyamide structure represented by the following general formula (1), which is a base polymer of the positive photosensitive resin composition of the present invention, Although there is no restriction | limiting in particular as the structure, In order to control alkali solubility, you may have a structure represented by following General formula (10). Moreover, it is preferable that the structure of following General formula (4) is included from a transparency viewpoint of i line | wire area | region, and a soluble viewpoint to the alkaline developing solution of an exposure part.

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, Y ₁ is a divalent organic group having at least 2 carbon atoms, and m ₁ is 1 It is an integer of ~ 1000. }

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently 2 having at least 2 carbon atoms. M ₁ is an integer of 1 to 1000, m ₂ is an integer of _{1 to} 500, m ₁ / (m ₁ + m ₂ )> 0.5, and X ₁ and The arrangement order of m ₁ units including Y ₁ and m ₂ units including X ₂ and Y ₂ is not limited. }

｛式中、Ｘ_３は、単結合、及び下記一般式（５）で表される構造からなる群より選ばれる少なくとも一種の構造を示し、Ｌ_１、Ｌ_２、及びＬ_３は、各々独立に、水素原子又はメチル基を示し、そしてＬ_４は、水素原子、メチル基又は水酸基を表す。｝

{Wherein X ₃ represents a single bond and at least one structure selected from the group consisting of structures represented by the following general formula (5), and L ₁ , L ₂ , and L ₃ are each independently , Represents a hydrogen atom or a methyl group, and L ₄ represents a hydrogen atom, a methyl group or a hydroxyl group. }

Furthermore, in the structure represented by the general formula (4), the tricyclodecane moiety is preferably at least one selected from the structural group represented by the following general formula (8).

Among them, the following general formula (9) is particularly preferable.

First, (A) the structure having a PBO precursor which is a unit containing X ₁ and Y ₁ in the structures represented by the general formula (1) and the general formula (7) will be described. The dihydroxydiamide unit has a structure obtained by polycondensation of a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure. The two groups of amino groups and hydroxy groups of the bisaminophenol are in ortho positions to each other, and the hydroxypolyamide is closed by heating to about 250 to 400 ° C. to form polybenz, which is a heat-resistant resin. Change to oxazole. X ₁ is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms. Y ₁ is preferably a divalent organic group having 2 or more and 30 or less carbon atoms. m ₁ is in the range of ₁ to 1000, preferably in the range of 2 to 100, and more preferably in the range of 3 to 60.

In the structure represented by the general formula (1), the hydroxy polyamide may have m ₂ diamide units of the general formula (7) as necessary. The diamide unit has a structure obtained by polycondensing a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of Y ₂ (COOH) ₂ . m ₂ is preferably in the range of 1 to 500, 1 to 10 more preferably in the range of.
In the structure represented by the general formula (1), the higher the ratio of the dihydroxydiamide unit in the hydroxypolyamide, the better the solubility in an alkaline aqueous solution used as a developer. Therefore, m ₁ / (m ₁ + m The value of ₂ ) is preferably 0.5 or more, more preferably 0.7 or more, and most preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis -(4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino- 3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1 , 3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.

Of these bisaminophenols having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , X ₁ is preferably an aromatic group selected from the following.

｛式中、Ｘ_４は、少なくとも２個以上の炭素原子を有する４価の有機基であり、前述したＸ_１で示される有機基として好ましいものからなる群から選択される少なくとも１つの有機基であることが好ましい。｝で示されるジアミンが挙げられる。 In addition, as a compound having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “PBO precursor structure in the molecule”). Can also be used. For example, the following general formula, which is obtained by reacting bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ with two molecules of nitrobenzoic acid for reduction, is given below:

{In the formula, X ₄ is a tetravalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups represented by X ₁ described above. Preferably there is. } Is mentioned.

｛式中、Ｙ_３は、少なくとも２個以上の炭素原子を有する２価の有機基であり、後述するＹ_１で示される有機基として好ましいものからなる群から選択される少なくとも１つの有機基であることが好ましい。｝で示されるジアミンを得る方法もある。 As another method for obtaining a diamine having a PBO precursor structure in the molecule, the dicarboxylic acid dichloride having the structure of Y ₃ (COCl) ₂ is reacted with two molecules of nitroaminophenol for reduction, and the following general formula:

{Wherein Y ₃ is a divalent organic group having at least 2 carbon atoms, and is an at least one organic group selected from the group consisting of preferable organic groups represented by Y ₁ described later. Preferably there is. } There is also a method for obtaining a diamine represented by:

Examples of the diamine having the structure of X ₂ (NH ₂ ) ₂ include aromatic diamine and silicon diamine.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diamino Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, 4,4 '-Diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines is at least one selected from the group consisting of chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, cyano group, and phenyl group And a compound substituted by a group or an atom.

Moreover, in order to improve adhesiveness with a base material, a silicon diamine can be selected as a part or all of the diamine having the structure of X ₂ (NH ₂ ) ₂ , and examples thereof include bis (4-amino Phenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyl) Dimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and the like.

｛式中、Ａ_１は、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、及び単結合からなる群から選択される２価の基を示し、Ｌ_７は、それぞれ独立に、水素原子、アルキル基、不飽和基、及びハロゲン原子からなる群から選択される基を示し、そしてｋは０〜４の整数を示す。｝ Examples of the dicarboxylic acid having Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures include dicarboxylic acids in which Y ₁ and Y ₂ are each an aromatic group or an aliphatic group selected from the following.

{In the formula, A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. L ₇ represents a selected divalent group, each L ₇ independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an unsaturated group, and a halogen atom, and k is an integer of 0 to 4 Indicates. }

｛式中、Ｌ_８、Ｌ_９及びＬ_１０は、各々独立に、水素原子又はメチル基を示し、そしてＬ_１１は、水素原子、メチル基又は水酸基を表す。｝。
上記した基において、得られる樹脂膜の機械物性が良好である点で、Ｌ_８、Ｌ_９、Ｌ_１０及び、Ｌ_１１が水素原子であることが最も好ましい。

{In the formula, L ₈ , L ₉ and L ₁₀ each independently represent a hydrogen atom or a methyl group, and L ₁₁ represents a hydrogen atom, a methyl group or a hydroxyl group. }.
In the above group, L ₈ , L ₉ , L ₁₀ and L ₁₁ are most preferably hydrogen atoms in that the mechanical properties of the resulting resin film are good.

Representative compounds as the dicarboxylic acid having a tricyclodecane skeleton, and a bis (carboxy) tricyclo [5,2,1,0 ^2,6] decane. The compound can be synthesized by the synthesis method according to Production Example A of JP-A No. 58-110538, the synthesis method according to Example 1 of JP-T No. 2002-504891, or the synthesis by Synthesis Example 2 of JP-A No. 09-15846. Can be obtained according to the method. However, in this method, since a heavy metal is used as an oxidizing agent, the following manufacturing method is more preferable in that no heavy metal is used. That is, tricyclo (5,2,1,0) decanedimethanol (catalog No. T0850 manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in acetonitrile or the like, and 2,2,6,6-tetramethylpiperidine-1-oxyl (hereinafter, referred to as “Catalyst No. T0850”) was dissolved. (Also referred to as “TEMPO”), and adjusting pH using disodium hydrogen phosphate, sodium dihydrogen phosphate, etc., and adding sodium chlorite and sodium dichlorite to oxidize, is a compound in the purification bis (carboxy) tricyclo can [5,2,1,0 ^2,6] to produce decane.

Other than the above-mentioned compounds, other dicarboxylic acid compounds having the structure of the above structural group (11) are methylcyclopentadiene dimer (catalog No. M0920 manufactured by Tokyo Chemical Industry), 1-methyldicyclopentadiene (Tokyo Chemical Industry). Catalog No. M0910) and 1-hydroxydicyclopentadiene (Tokyo Chemical Industry catalog No. H0684) as raw materials. Org. Chem. , 45, 3527 (1980), hydrogen bromide or hydrogen chloride is added to the unsaturated bond site of the raw material. Am. Chem. Soc. , 95,249 (1973) according to methods known in the further carbon monoxide, tricyclo by an addition of water [5,2,1,0 ^2,6] two hydroxymethyl groups decane skeleton introduced can do. Other methods for synthesizing dihydroxymethyl compounds include those described in J. Org. Am. Chem. Soc. , 91,2150 (1969), 9-borabicyclo (3,3,1) nonane is added to the unsaturated bond site to form an intermediate, and then reacted with carbon monoxide to form LiAlH. A dihydroxymethyl compound can also be produced by reduction with (OCH ₃ ) ₃ . According to this manner, the dihydroxymethyl body obtained by bis (carboxy) tricyclo [5,2,1,0 ^2,6] method described in decane, to oxidize in the same manner dihydroxy methyl group, object The dicarboxylic acid can be obtained.

In addition, a derivative of 5-aminoisophthalic acid can be used for a part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures. Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene 2-acetyl chloride, p -Styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, 2-ethoxy chloroformate Ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloro Acid 2,2,2-trichloroethyl ester, chloroformate-2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, isobornylbenzyl chloroformate, Chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-tert-butyl-dicarbonate N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisila N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanic acid Examples include phenyl, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride.

｛式中、Ａ_２は、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ_３）_２−からなる群から選択される２価の基を意味する。｝。 Furthermore, as a dicarboxylic acid having a Y ₁ (COOH) _{2 or} Y ₂ (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can also be used. Examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and benzyl alcohol. Examples of monoamine include butylamine and aniline. As an example of said tetracarboxylic dianhydride, the compound shown by following Chemical formula is mentioned.

{Wherein A ₂ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. A divalent group is meant. }.

｛式中、Ｘ_５は、Ｘ_１（ＯＨ）_２（ＮＨ−）_２で表される２価の有機基を表し、そしてＸ_１は、上記一般式（１）におけると同義である。｝で示される化学式が挙げられる。 Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.
Also, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also. The tetracarboxylic dianhydride obtained here has the following chemical formula:

{Wherein X ₅ represents a divalent organic group represented by X ₁ (OH) ₂ (NH—) ₂ , and X ₁ has the same meaning as in General Formula (1). } Is given.

  As a method of polycondensation of the dicarboxylic acid and bisaminophenol (diamine) for synthesizing hydroxypolyamide, diacid chloride and thionyl chloride are used to form diacid chloride, and then bisaminophenol (diamine) is used. And a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

  In the hydroxy polyamide having the repeating unit represented by the general formula (1), it is also preferable to use the terminal group after being sealed with an organic group (hereinafter referred to as “sealing group”). In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excessive number of moles compared to the sum of the bisaminophenol component and the diamine component, a compound having an amino group or a hydroxyl group is used as the sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate and the like.

  Conversely, when the sum of the bisaminophenol component and the diamine component is used in an excessive number of moles compared to the dicarboxylic acid component, the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound. Examples of the compound include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methylcyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosylic chloride and the like.

  The base polymer of the photosensitive resin composition may be used only with the above-mentioned hydroxypolyamide, but it can be obtained by cyclocondensing tetracarboxylic dianhydride and an aromatic diamine having a phenolic hydroxyl group. A polyimide structure having a phenolic hydroxyl group can be copolymerized as necessary.

  From the viewpoint of solvent solubility, the tetracarboxylic dianhydride when synthesizing a polyimide containing a phenolic hydroxyl group has an aromatic tetracarboxylic dianhydride having 8 to 36 carbon atoms and 6 to 34 carbon atoms. Preferred are compounds selected from alicyclic tetracarboxylic dianhydrides. Specifically, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, pyromellitic dianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4'-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -ter-phenyl tetracarboxylic dianhydride, 3,3 '' ', 4,4' ''-qua Quater-phenyl tetracarboxylic dianhydride, 3,3 ″ ″, 4,4 ″ ″-quinque-phenyl phenyltetracarboxylic dianhydride, 2,2 ′, 3 , 3′-biphenyltetracarboxylic dianhydride, methyle 4,4′-diphthalic dianhydride, 1,1-ethylidene-4,4′-diphthalic dianhydride, 2,2-propylidene-4,4′-diphthalic dianhydride, 1,2 -Ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, , 5-pentamethylene-4,4′-diphthalic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, thio-4,4′-diphthalic dianhydride, sulfonyl-4,4 '-Diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4- Bis (3,4-dicarboxyphenoxy) benzene dianhydride, , 3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene Anhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3 -(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) ) Dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic Dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4 Butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, Cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4′-bis (cyclohexane Xanthane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4′-bis (cyclohexane-) 1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4′-bis ( Cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4′-bis (cyclohexane-1,2- Dicarboxylic acid) dianhydride, sulfonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6 -Tetracarboxylic dianhydride, el- [1S, 5R, 6R] -3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis (3,4-dicarboxylic anhydride phenyl) ether Among them, among them, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, bis (3,4-dicarboxyphenyl) ether Preferred are dianhydrides, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride). Among them, 5- (2,5-dioxotetrahydro-3-furyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride are among them. From the viewpoint of transparency with respect to i-line of a mercury lamp, solubility in an alkaline aqueous solution, and photosensitivity are preferable.

Diamines having a phenolic hydroxyl group represented by X ₃ to be used in synthesizing the imide unit having a phenolic hydroxyl group, (when n = 2) above phenolic diamine or non-phenolic diamine (n = 0, )) Or 2,4-diaminophenol (when n = 1). Among these, 2,2-bis (3-amino-4-hydroxyphenyl) propane is more preferable from the viewpoint of high photosensitivity of the resin composition.

  The dehydration condensation reaction when synthesizing an imide unit having a phenolic hydroxyl group is carried out by, for example, following the method described in International Publication No. 01/034679 pamphlet with the above tetracarboxylic dianhydride and the above phenolic diamine. The reaction can be carried out by heating at 30 ° C. to 220 ° C., preferably 170 ° C. to 200 ° C. in the presence of a base catalyst. As the acid catalyst, it is possible to use an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid that is usually used in the production of polyimide. γ-valerolactone and pyridine may be used. Base catalysts include pyridine, triethylamine, dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) undecene-7, 1,3,5,7-tetraazatricyclo (3,3,1,1, 3,7) Decane, triethylenediamine or the like may be used.

Furthermore, without adding a polycondensation catalyst or the like, the temperature of the reaction solution is maintained at a temperature higher than the temperature at which the imidization reaction occurs, and the water generated by the dehydration reaction is removed from the reaction system using an azeotropic solvent with water such as toluene. Alternatively, the imidation dehydration condensation reaction may be completed.
As a reaction solvent for performing the dehydration condensation reaction, it is preferable to use a polar organic solvent for dissolving an alkali-soluble resin soluble in an aqueous alkali solution in addition to toluene, which is a solvent for azeotropically distilling water. As these polar solvents, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane and the like are used.
In the production of polyimide, the solubility and physical properties in an alkaline aqueous solution may be controlled by copolymerizing the above-mentioned non-phenolic diamine in addition to the above-mentioned phenolic diamine as necessary.
When two or more tetracarboxylic dianhydrides or two or more phenolic diamines or non-phenolic diamines are used, a block copolycondensate using a sequential reaction may be used, or a raw material having three or more components is charged. In addition, the raw materials may be charged into the reaction system at the same time to form a random copolycondensate.
The base polymer of the positive photosensitive resin composition of the present invention may copolymerize the above-mentioned hydroxypolyamide and polyimide unit, but the copolymerization ratio at the time of copolymerization is arbitrarily selected, but polybenzoxazole The ratio of the precursor unit: polyimide unit is preferably in the range of 10:90 to 100: 0 from the viewpoint of photosensitivity.

｛式中、Ｌ_５は、−ＣＨ_２−、−Ｏ−、及び−Ｓ−からなる群から選択される基を示し、そしてＬ_６は、水素原子又はアルキル基を示す。｝。 (A) The terminal of the aqueous alkali solution-soluble polymer is preferably at least one terminal group selected from the group consisting of terminal groups represented by the following general formula (9).

{Wherein L ₅ represents a group selected from the group consisting of —CH ₂ —, —O—, and —S—, and L ₆ represents a hydrogen atom or an alkyl group. }.

  You may modify not only the said General formula (6) but with the following end group. Examples of the method for modifying the terminal include maleic anhydride, succinic anhydride, cinnamic anhydride, 5-norbornenic anhydride, 4-ethynylphthalic anhydride, phenylethynylphthalic anhydride, 3,6- Epoxy-1,2,3,6-tetrahydrophthalic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic An appropriate amount of acid anhydride, 4-aminostyrene, 4-ethynylaniline, 3-ethynylaniline, 4-aminophenol, 3-aminophenol, 2-aminophenol or the like may be added during the synthesis of the alkali-soluble resin. Moreover, you may leave the dicarboxylic acid used by this invention as a terminal.

  (A) The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of an aqueous alkali-soluble polymer is preferably 3,000 to 50,000, and preferably 6,000 to 30,000. Is more preferable. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern. Moreover, from a viewpoint of resolution, 50,000 or less is preferable. As developing solvents for GPC, tetrahydrofuran (hereinafter also referred to as “THF”) and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Photoacid generator (B) As the photoacid generator, a naphthoquinonediazide compound, an onium salt, a halogen-containing compound, and the like can be used. From the viewpoint of solvent solubility and storage stability, a naphthoquinonediazide structure is used. (Hereinafter, also referred to as “naphthoquinone diazide compound”) is preferable.
Examples of the onium salt include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, and diazonium salts, and onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts are preferable. .
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable.

  The naphthoquinone diazide compound is a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure. US Pat. No. 2,772,972, US Pat. No. 2,797,213 And U.S. Pat. No. 3,669,658. The naphthoquinonediazide structure includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. At least one compound selected from the group consisting of (hereinafter also referred to as “NQD compound”).

  The NQD compound can be obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride and subjecting the resulting naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound according to a conventional method. For example, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran, and basic such as triethylamine It can be obtained by reacting in the presence of a catalyst for esterification and washing the resulting product with water and drying.

｛式中、ｎ_２〜ｎ_５は、それぞれ独立に、１又は２を示し、Ｒ_１〜Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アリル基、及びアシル基からなる群から選択される少なくとも１つの１価の基を示し、Ｙ_４〜Ｙ_６は、それぞれ独立に、単結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＯ_２−、シクロペンチリデン、シクロヘキシリデン、フェニレン、及び下記化学式で示される有機基からなる群から選択される少なくとも１つの２価の基を示す。｝ Preferred NQD compounds are described below.
NQD compounds of polyhydroxy compounds represented by the following general formula (10)

{Wherein n _{2 to} n ₅ each independently represent 1 or 2, and R _{1 to} R ₁₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, And at least one monovalent group selected from the group consisting of an acyl group, and Y _{4 to} Y ₆ each independently represent a single bond, —O—, —S—, —SO—, —SO ₂ —. , —CO—, —CO ₂ —, cyclopentylidene, cyclohexylidene, phenylene, and at least one divalent group selected from the group consisting of organic groups represented by the following chemical formulae. }

｛式中、Ｒ_１１及びＲ_１２は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリル基、及び置換アリル基からなる群から選択される少なくとも１つの１価の基を示す。｝

{Wherein R ₁₁ and R ₁₂ each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an allyl group, and a substituted allyl group. }

｛式中、Ｒ_１３〜Ｒ_１６は、水素原子又はアルキル基を示し、それぞれ同一でも相異なっていてもよく、そしてｍ_３は、１〜５の整数を示す。｝

{In formula, R < ₁₃ > -R < ₁₆ > shows a hydrogen atom or an alkyl group, may be same or different, respectively, and m < ₃ > shows the integer of 1-5. }

｛式中、Ｒ_１７〜Ｒ_２０は、水素原子又はアルキル基を示し、それぞれ同一でも相異なっていてもよい。｝。

{In formula, R < ₁₇ > -R < ₂₀ > shows a hydrogen atom or an alkyl group, and may be same or different, respectively. }.

Specific examples of the compound include NQD compounds of polyhydroxy compounds described in [Chemical Formula 18] to [Chemical Formula 32] of JP-A No. 2001-109149.
Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

｛式中、Ｘ_６は、下記化学式で表される有機基から選ばれる少なくとも１つの４価の基を示し、Ｒ_２１〜Ｒ_２４は、それぞれ独立に、１価の有機基を示し、ｌは、０又は１を示し、ｍ_４〜ｍ_７は、それぞれ独立に、０〜３の整数を示し、そしてｎ_６〜ｎ_９は、それぞれ独立に、０〜２の整数を示す。｝ NQD compounds of polyhydroxy compounds represented by the following general formula (11)

{In the formula, X ₆ represents at least one tetravalent group selected from organic groups represented by the following chemical formulas; R _{21 to} R ₂₄ each independently represents a monovalent organic group; , 0 or 1, m _{4 to} m ₇ each independently represents an integer of 0 to 3, and n _{6 to} n ₉ each independently represents an integer of 0 to 2. }

Specific compounds are described in [Chemical Formula 23] to [Chemical Formula 28] of JP-A No. 2001-092138. Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

｛式中、ｍ_８は、３〜８の整数を示し、ｍ_８×ｊ個のＬ_１４は、それぞれ独立に、１個以上の炭素原子を有する１価の有機基を示し、ｊは１〜５の整数を示し、ｍ_８個のＬ_１２、及びｍ_８個のＬ_１３は、それぞれ独立に、水素原子又は１価の有機基からなる群から選択される１価の基を示す。｝ NQD compounds of polyhydroxy compounds represented by the following general formula (12)

{In the formula, m ₈ represents an integer of 3 to 8, m ₈ × j L _{14 s} each independently represent a monovalent organic group having one or more carbon atoms, and j represents 1 to 1 5 of an integer, m ₈ pieces of L _12, and m ₈ pieces of L ₁₃ each independently represent a monovalent group selected from the group consisting of a hydrogen atom or a monovalent organic group. }

｛式中、ｐは、０〜９の整数である。｝。 Specific preferred examples are described in [Chemical Formula 24] and [Chemical Formula 25] of JP-A-2004-347902.
Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

{Wherein p is an integer of 0-9. }.

｛式中、Ｍ_２は、脂肪族の３級又は４級炭素を含む２価の有機基を示し、そしてＡ_３は、下記の化学式で表される基から選ばれる少なくとも１つの２価の基を示す。｝

NQD compounds of polyhydroxy compounds represented by the following general formula (13)

{Wherein M ₂ represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and A ₃ represents at least one divalent group selected from the groups represented by the following chemical formulas: Indicates. }

Specific compounds are described in [Chemical Formula 22] to [Chemical Formula 28] of JP-A No. 2003-131368.
Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

｛式中、Ｌ_１５は、−ＣＨ_２−、−Ｏ−、及び−Ｓ−からなる群から選択される基を示し、そしてＬ_１６は、水素原子又はアルキル基を示す。｝

{Wherein L ₁₅ represents a group selected from the group consisting of —CH ₂ —, —O—, and —S—, and L ₁₆ represents a hydrogen atom or an alkyl group. }

｛式中、Ｌ_１７は、−ＣＨ_２−、−Ｏ−、及び−Ｓ−からなる群から選択される基を示し、そしてＬ_１８は、水素原子又はアルキル基を示す。｝

{Wherein L ₁₇ represents a group selected from the group consisting of —CH ₂ —, —O—, and —S—, and L ₁₈ represents a hydrogen atom or an alkyl group. }

｛式中、Ｒ_２５〜Ｒ_２７は、下記の一般式で表される１価の有機基を示し、それぞれ同じであっても異なっていてもよく、そしてｍ_９〜ｍ_１１は、それぞれ独立に、０〜２の整数である。｝ NQD compounds of polyhydroxy compounds represented by the following general formula (14)

{Wherein R _{25 to} R ₂₇ represent a monovalent organic group represented by the following general formula, and may be the same or different, and m _{9 to} m ₁₁ are each independently , An integer of 0-2. }

｛式中、Ｒ_２８は、それぞれ独立に、水素原子、アルキル基、及びシクロアルキル基から選ばれる少なくとも１つの１価の有機基を示し、そしてｍ_１２は、それぞれ独立に、０〜２の整数である。｝。

{In the formula, each R ₂₈ independently represents at least one monovalent organic group selected from a hydrogen atom, an alkyl group, and a cycloalkyl group; and m ₁₂ each independently represents an integer of 0 to 2. It is. }.

Specific examples of the compound include NQD compounds of polyhydroxy compounds described in [Chemical Formula 17] to [Chemical Formula 22] of JP-A No. 2004-109849.
Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

｛式中、Ｒ_２９は、水素原子、アルキル基、アルコキシ基、及びシクロアルキル基から選ばれる少なくとも１つの１価の有機基を示す。｝。 NQD compounds of polyhydroxy compounds represented by the following general formula (15)

{Wherein R ₂₉ represents at least one monovalent organic group selected from a hydrogen atom, an alkyl group, an alkoxy group, and a cycloalkyl group. }.

Specific compounds are described in [Chemical Formula 18] to [Chemical Formula 22] of JP-A No. 2001-356475.
Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

｛式中、Ｒ_３０は、下記の一般式で表される１価の有機基を示し、それぞれ同じであっても異なっていてもよく、ｍ_１３〜ｍ_１５は、それぞれ独立に、０〜２の整数を示し、Ｒ_３１〜Ｒ_３３は、水素原子、アルキル基又はシクロアルキル基の内から選ばれる１つを示す。｝ NQD compounds of polyhydroxy compounds represented by the following general formula (16)

{In the formula, R ₃₀ represents a monovalent organic group represented by the following general formula, and may be the same or different, and m _{13 to} m ₁₅ are each independently 0 to 2 R _{31 to} R ₃₃ represent one selected from a hydrogen atom, an alkyl group, or a cycloalkyl group. }

｛式中、Ｒ_３４は、それぞれ独立に、水素原子、アルキル基及びシクロアルキル基から選ばれる少なくとも１つの１価の有機基を示し、そしてｍ_１６は、０〜２の整数を示す。｝。

{In the formula, each R ₃₄ independently represents at least one monovalent organic group selected from a hydrogen atom, an alkyl group and a cycloalkyl group; and m ₁₆ represents an integer of 0 to 2. }.

Specific examples of the compound include NQD compounds of polyhydroxy compounds described in [Chemical 15] and [Chemical 16] of JP-A-2005-008626.
Among these, NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the positive photosensitive resin composition.

Specifically, other structures are preferably as follows.

  In the present composition, as the naphthoquinone diazide sulfonyl group in the NQD compound, both a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are preferably used. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination. In the present composition, the blending amount of the naphthoquinone diazide compound with respect to the aqueous alkali-soluble polymer is 1 to 50 parts by weight, preferably 5 to 30 parts by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer. If the blending amount of the photosensitive diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good. On the other hand, if it is 50 parts by mass or less, the tensile elongation of the cured film is good and the development residue in the exposed part (Scum) is low.

｛式中、Ｄ_１は、水素原子、炭素数１〜６のアルキル基、アルケニル基、及び架橋し得る有機基からなる群より選ばれる官能基を少なくとも１つ有し、Ｍ_１は、−ＣＨ_２−、−Ｏ−、及び−Ｓ−からなる群から選択される基を示し、Ｚ_１は、２価の有機基であり、ｎ_１は、０〜４の整数であり、そしてＤ_１が複数ある場合、複数のＤ_１は同じでも異なっていてもよい。｝ (C) As a compound represented by following General formula (2), a bisallyl nadiimide compound, a bisnorbornene imide compound, etc. are mentioned. From the viewpoint of sensitivity, a compound consisting of the following general formula (3) is more preferable.
Specific examples of these compounds include general formula (3) (manufactured by Maruzen Petrochemical Co., Ltd .: trade names: BANI-M, BANI-X, BANI-H, BANI-D). Of the compounds represented by the general formula (3), BANI-X is most preferable from the viewpoint of the curing shape and sensitivity.

{In the formula, D ₁ has at least one functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an organic group that can be cross-linked, and M ₁ represents —CH ₂ represents a group selected from the group consisting of —O— and —S—, Z ₁ is a divalent organic group, n ₁ is an integer of 0 to 4, and D ₁ is When there are a plurality, D ₁ may be the same or different. }

(C) A compound may be used individually or may be used in mixture of 2 or more.
(C) The compounding quantity of a compound is 1-40 mass parts with respect to 100 mass parts of (A) alkali aqueous solution soluble polymer, 2-30 mass parts is more preferable, and 4-20 mass parts is still more preferable. When the compounding amount of the compound is 1 part by mass or more, the cured shape at the time of curing is improved. On the other hand, when the compounding amount is 40 parts by mass or less, the tensile elongation of the film after curing is good and the adhesiveness and litho performance are good. Show.

(D) Organic solvent In the present invention, these components are preferably dissolved in a solvent to form a varnish and used as a solution of the photosensitive resin composition. Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide (hereinafter also referred to as “DMAc”). ), Dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as “DMDG”), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol Seteto, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, may be used alone or as a mixture of methyl 3-methoxy propionate or the like. Of these solvents, non-amide solvents are preferred because they have little influence on the photoresist. Specific preferred examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol and the like. These organic solvents may be used alone or in combination of two or more.
(D) The compounding quantity in the case of mix | blending a solvent is 100-2000 mass parts with respect to 100 mass parts of (A) alkali aqueous solution soluble polymer, and a viscosity can be controlled by changing the addition amount of an organic solvent. . It is preferably 100 to 1000 parts by mass, and more preferably 100 to 1000 parts by mass, and the addition amount of the solvent can be set to a viscosity suitable for the coating apparatus and the coating thickness within the above range. It is preferable because the manufacturing can be facilitated.

(E) Other additives The photosensitive resin composition is known as an additive for a hydroxyl group-containing compound (excluding a phenol compound that appears later) and a positive photosensitive resin composition, if necessary. It is also possible to add a phenol compound, a dye, a surfactant, a stabilizer, at least one kind of an adhesion assistant for enhancing the adhesion to the silicon wafer.
More specifically describing the additive, the hydroxyl group-containing compound preferably has 4 to 14 carbon atoms. Addition of a hydroxyl group-containing compound to the photosensitive resin composition of the present invention is preferable from the viewpoints of sensitivity and resolution. Specific examples of the hydroxyl group-containing compound include cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, and 4-ethylcyclohexanol. 4-t-butyrocyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1-propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, norbornane-2-methanol, cyclooctanol, 2 , 3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4-heptene-1- All, cis-3-oct N-1-ol, 4-ethyl-1-octin-3-ol, 2,7-octadienol, 3,6-dimethyl-1-heptin-3-ol, 3-ethyl-2-methyl-3- Pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol, trans, cis-2,6-nonadien-1-ol, 1-nonene-3 -Ol, cis-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,5-hexadiene-3,4 -Diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,2,4,4-tetramethyl -1,3-cyclo Butanediol, 1,2-cyclohexanediol, trans-p-menthane-3,8-diol, 2,4-dimethoxybenzyl alcohol, butyroin, and the like.

Among these, 2,3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans-2-hepten-1-ol, cis-4 -Hepten-1-ol, cis-3-octen-1-ol, trans, cis-2,6-nonadien-1-ol, cis-2-butene-1,4-diol, 1,5-hexadiene-3 Hydroxyl group-containing compounds having an unsaturated bond or a branched structure such as 1,4-diol are preferable, and monoalcohols are preferable from diols from the viewpoint of adhesion to the substrate, and among them, 2,3,4-trimethyl-3-pen Particularly preferred are tanol, 3-ethyl-2-methyl-3-pentanol, and glycerol-α, α′-diallyl ether.
These hydroxyl group-containing compounds may be used alone or in combination of two or more.
The blending amount in the case of blending the above hydroxyl group-containing compound is preferably 0 to 70 parts by weight, more preferably 0.1 to 50 parts by weight, and 1 to 40 parts by weight with respect to 100 parts by weight of the aqueous alkaline solution polymer. Part is more preferable, and 5 to 25 is particularly preferable. When the compounding amount of the hydroxyl group-containing compound is 0.01 parts by mass or more, the development residue in the exposed part is reduced, while when it is 70 parts by mass or less, the tensile elongation of the film after curing is good.

Examples of the phenol compound include ballast agents, paracumylphenol, bisphenols, resorcinols, linear phenolic compounds such as MtrisPC and MtetraPC used in the photosensitive diazoquinone compound (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TrisP. -Non-linear phenolic compounds such as HAP, TrisP-PHBA, TrisP-PA (made by Honshu Chemical Industry Co., Ltd .: trade name), compounds in which 2-5 hydrogen atoms of the phenyl group of diphenylmethane are substituted with hydroxyl groups, 2, 2 -The compound etc. which substituted the 1-5 hydrogen atom of the phenyl group of diphenylpropane by the hydroxyl group are mentioned. By adding the phenol compound, the adhesion of the relief pattern during development can be improved and the generation of residues can be suppressed. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned photosensitive diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester.
0-50 mass parts is preferable with respect to 100 mass parts of this aqueous alkali solution, and 1-30 mass parts is preferable with respect to 100 mass parts of this aqueous alkali solution. When the addition amount is within 50 parts by mass, the heat resistance of the film after thermosetting is good.
Examples of the dye include methyl violet, crystal violet, and malachite green. As for the compounding quantity in the case of mix | blending dye, 0.1-10 mass parts is preferable with respect to 100 mass parts of this alkaline aqueous solution soluble polymer. When the addition amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

Examples of the surfactant include polypropylene glycol, polyglycols such as polyoxyethylene lauryl ether, and nonionic surfactants made of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (manufactured by Sumitomo 3M: trade name), MegaFac (manufactured by Dainippon Ink & Chemicals, Inc .: trade name), or Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.) can be used. Furthermore, organosiloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name), and the like can be mentioned. By adding the surfactant, it is possible to make it less likely to cause repellency of the coating film at the wafer edge during coating.
0-10 mass parts is preferable with respect to 100 mass parts of this aqueous alkali solution, and, as for the compounding quantity in the case of mix | blending surfactant, 0.01-1 mass part is more preferable. If the addition amount is within 10 parts by mass, the heat resistance of the film after thermosetting is good.
Examples of the adhesion aid include various silane coupling agents such as alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, and epoxy silane.

  Specific preferred examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Syra Ace S810), 3-mercaptopropyltriethoxysilane. (Manufactured by Azmax Co., Ltd .: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, product of Azmax Co., Ltd .: trade name SIM6474.0), Azmax Co., Ltd .: Trade name SIM6473.5C), Mercaptomethylmethyldimethoxysilane (Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-me Captopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2 -Mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2 -Mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutylto Limethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilyl) Propyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilyl) Propyl) urea, N- (3 Methoxydipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tri Propoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-tri Methoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmax Corporation) SLA0598.0), m-aminophenyltrimethoxysilane (Manufactured by AZMAX Co., Ltd .: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by AZMAX Co., Ltd .: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by AZMAX Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: trade name SIT83396.), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) ) Pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, and the like. Particularly preferable examples include, but are not limited to, the following structures.

The blending amount in the case of blending the adhesion aid is preferably 0 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and 0.1 to 8 parts by weight with respect to 100 parts by weight of the alkaline aqueous solution-soluble polymer. Part is more preferable, and 1 to 6 parts by mass is particularly preferable. When the compounding amount of the silicon-based coupling agent is 0.01 parts by mass or more, there is no development residue in the exposed part, and the adhesiveness with the silicon substrate is good. Good stability.
Further, the following compounds may be used in combination. Specifically, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis ( Methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxy Silyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfur Bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, bis (pentadionate) titanium-O, O'- And bis (oxyethyl) -aminopropyltriethoxysilane. Of these, tetramethoxysilane and tetraethoxysilane are particularly preferable. The blending amount of the above compound with respect to the aqueous alkali-soluble polymer is preferably 0 to 10 parts by weight, more preferably 0.1 to 6 parts by weight, and 1 to 4 parts by weight with respect to 100 parts by weight of the aqueous alkali-soluble polymer. Particularly preferred. When it is 0.1 part by mass or more, there is no development residue in the exposed part and the adhesiveness to the silicon substrate is good, while when it is 10 parts by mass or less, the temporal stability in the adhesiveness is good.

In addition to the above-mentioned compound (C), the photosensitive resin composition can contain a crosslinking agent. As the crosslinking agent, a compound that causes a crosslinking reaction with the alkali-soluble resin by heat is used. Here, as a temperature which raise | generates a crosslinking reaction, 150-350 degreeC is preferable. The crosslinking reaction occurs during the heat treatment after pattern formation by development. For the purpose of improving chemical resistance and physical properties, it is preferable to add the following compounds.

Besides the above crosslinking agents, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycidylamine type epoxy resin, polysulfide type epoxy resin, MX270 (Sanwa) Chemical Co., Ltd.), MX280 (manufactured by Sanwa Chemical Co., Ltd.), dimethylol urea, trimethylol melamine, hexamethylol melamine, dimethylol ethylene urea, dimethylol propylene urea, 1,4-bis (methoxyphenoxy) benzene, trimethoxymethyl melamine , Hexamethoxymethyl melamine, diethylene glycol diallyl ether, diallyl chlorendate, diallyl hexahydrophthalate, and the like. Of these, compounds having an alkoxymethyl group and an allyl ester group are preferred from the viewpoint of storage stability. Among them, a compound having an alkoxymethyl group is used as a cyclized resin as a base polymer used in the photosensitive resin composition. This is most preferable in terms of the effect of reducing deformation during the process.
The blending amount when the crosslinking agent component is blended is 0.5 to 50 with respect to 100 parts by mass of the aqueous alkali-soluble polymer from the viewpoint of deformation of the pattern in the heat treatment of development and the allowable width of the residue generated during development. A mass part is preferable and 5-20 mass parts is more preferable.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, the manufacturing method of the cured relief pattern of the present invention will be specifically described below.
(1) A step of forming a photosensitive resin layer made of a photosensitive resin composition on a substrate (first step).
The photosensitive resin composition solution is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spinner or a coater such as a die coater or a roll coater. This is dried by applying heat at 50 to 140 ° C., preferably 100 to 140 ° C., using an oven or a hot plate to remove the solvent (hereinafter also referred to as “soft baking” or “pre-baking”).
(2) A step of exposing with actinic radiation through a mask or directly irradiating a light beam, an electron beam or an ion beam (second step).
Subsequently, the photosensitive resin layer is exposed to actinic radiation through a mask using a contact aligner or a stepper, or directly irradiated with a light beam, an electron beam or an ion beam. As the actinic ray, g-line, h-line, i-line, or KrF laser can also be used.
(3) A step of eluting or removing the exposed portion or irradiated portion (third step).
Next, the exposed portion or the irradiated portion is dissolved and removed with a developer, and then rinsed with a rinse solution to obtain a desired relief pattern. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.
The developer used for developing the film formed of the photosensitive resin composition dissolves and removes the alkali-soluble polymer, and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia and the like.
Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.
Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.

(4) Step of heating the obtained relief pattern (fourth step)
Finally, the obtained relief pattern is heat-treated (hereinafter, this process is referred to as “cure”) to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used. As a heating method, heating by hot air, infrared rays, electromagnetic induction, or the like is recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C. The heating time is preferably 15 minutes to 8 hours, and more preferably 1 hour to 4 hours. The atmosphere is preferably in an inert gas such as nitrogen or argon.
A semiconductor device prepared using the photosensitive resin composition of the present invention has a cured relief pattern made of the photosensitive resin composition, a surface protective film, an interlayer insulating film, an insulating film for rewiring, and a protective film for flip chip devices. Or it can manufacture by combining with the manufacturing method of a well-known semiconductor device as a protective film of the apparatus which has a bump structure.
The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, and liquid crystal alignment films.

Hereinafter, the present invention will be described with reference examples and examples.
[Reference Example 1]
<Preparation of bis (carboxy) tricyclo [5,2,1,0 ^2,6] decane>
Teflon (registered trademark) glass separable three-necked flask equipped with anchor type agitator, tricyclo [5,2,1,0 ^2,6] decane dimethanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 71.9 g (0.366 mol) dissolved in 1 L of acetonitrile was added to the solution, and 256.7 g (1.808 mol) of disodium hydrogen phosphate and 217.1 g of sodium dihydrogen phosphate (1.4. 809 mol) was added. To this, 2.8 g (0.0179 mol) of 2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter also referred to as “TEMPO”) was added and dissolved by stirring. It was.
143.2 g (1.267 mol) of 80% sodium chlorite was diluted with 850 mL of ion-exchanged water and added dropwise to the reaction solution. Subsequently, 3.7 mL of 5% sodium dichlorite aqueous solution was diluted with 7 mL of ion-exchanged water and added dropwise to the reaction solution. This reaction solution was kept at 35 to 38 ° C. by a constant temperature layer and stirred for 20 hours to be reacted.

After the reaction, the reaction solution is cooled to 12 ° C., an aqueous solution in which 75 g of sodium sulfite is dissolved in 300 mL of ion-exchanged water is added dropwise to the reaction solution, the excess sodium chlorite is deactivated, and then with 500 mL of ethyl acetate. Washed. Thereafter, 115 mL of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 3 to 4, and the precipitate was collected by decantation. This precipitate was dissolved in 200 mL of tetrahydrofuran. The aqueous layer was extracted twice with 500 mL of ethyl acetate and then washed with brine, and the precipitate was dissolved in a tetrahydrofuran solution. The above tetrahydrofuran solution was mixed and dried over anhydrous sodium sulfate. The solution concentrated in an evaporator, followed by drying, to obtain a bis (carboxy) tricyclo [5,2,1,0 ^2,6] white crystalline product with decane 58.4 g (71.1% yield).

[Reference Example 2]
<Preparation of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane>
Bis obtained in Reference Example 1 (carboxy) tricyclo [5,2,1,0 ^2,6] decane 62.5 g (278 mmol), thionyl chloride 97 mL (1.33 mol), pyridine 0.4mL of (5.0 mmol) The reaction vessel was charged and stirred at 25 to 50 ° C. for 18 hours for reaction. After completion of the reaction, toluene was added, under reduced pressure, the excess thionyl chloride was concentrated by azeotroping with toluene, oily bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane 73.3 g (yield 100%) was obtained.

[Reference Example 3]
<Synthesis of aqueous alkali-soluble polymer>
In a 2 L separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 75.9 g (0.96 mol) of pyridine and 692 g of DMAc were added at room temperature. (25 ° C.) The mixture was stirred and dissolved. A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 88 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of dropping, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared.

Next, this was cooled to 8 ° C. with a water bath, and a solution obtained by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropping, the above reaction solution was dropped into 12 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried to obtain an alkali-soluble resin (P- 1) was obtained. The weight average molecular weight (Mw) by GPC (high performance liquid chromatography) of the alkali-soluble resin thus synthesized is a single sharp curve of 14000 in terms of polystyrene and is a single composition. The analysis conditions for GPC are described below.
Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

[Reference Example 4]
Bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter also referred to as “BAP”) is placed in a glass separable three-necked flask equipped with a Teflon (registered trademark) vertical stirrer. .) 69.17 g (268 mmol), NMP 276 g, and 12.7 g (160 mmol) of pyridine were added, a nitrogen introduction tube was attached to the flask, and the mixture was stirred while flowing nitrogen gas to dissolve BAP. After the BAP was dissolved, the reaction vessel was cooled by immersing it in a vessel in which dry ice was added to methanol. Bis prepared in Reference Example 2 (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane 69.99G (268 mmol) was dissolved in γ- butyrolactone 280 g, 30 maintained at -10 to-19 ° C. Minutes were added dropwise to the reaction vessel. After completion of the dropping, the reaction vessel was immersed in an ice bath and stirred at 2 ° C. for 2 hours. Further, 29.65 g (375 mmol) of pyridine was added.

Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 350 mL of NMP. Subsequently, ion exchange was performed with 78 g of cation exchange resin (Amberlyst A21, manufactured by Organo) and 75 g of anion exchange resin (Amberlyst 15, manufactured by Organo). This solution is dropped into 3 L of ion-exchanged water under high-speed stirring, the polymer is dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried, and an alkali-soluble resin (P-2) comprising a PBO precursor unit. Got. The weight average molecular weight by GPC of the alkali-soluble resin thus synthesized is a single sharp curve of 36800 in terms of polystyrene, and is a single composition. The analysis conditions for GPC are described below.
Column: Trade name Shodex 805M / 806M in series manufactured by Showa Denko Co., Ltd. Liquid separation: N-methylpyrrolidone 40 ° C
Flow rate: 1.0 ml / min Detector: Trade name RI-930, manufactured by JASCO Corporation

[Reference Example 5]
6FAP 91.56 g (250 mmol), DMAc 183 g, GBL 550 g, and pyridine 25 g (315 mmol) were placed in a glass separable three-necked flask equipped with a Teflon (registered trademark) saddle type stirrer to dissolve 6FAP. After 6FAP was dissolved, the reaction vessel was cooled by immersing it in a vessel in which dry ice was added to methanol. Bis prepared in Reference Example 2 (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane 62.02g of (238 mmol) was dissolved in γ- butyrolactone 186 g, 60 minutes at a constant temperature of. 5 to-20 ° C. Was added dropwise to the reaction vessel. After completion of the dropping, the reaction vessel was immersed in an ice bath and stirred at 2 ° C. for 2 hours. Further, 12.5 g (158 mmol) of pyridine was added.
The reaction solution was returned to room temperature, 12.312 g (75 mmol) of 5-norbornene acid anhydride and 5.93 g (75 mmol) of pyridine were added, immersed in a 50 ° C. hot water bath, the reaction solution was brought to 50 ° C. and stirred for 18 hours.

Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 470 g of GBL. Next, ion exchange was performed with 78 g of cation exchange resin and 95 g of anion exchange resin. This solution was dropped into 5 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried, and an aqueous alkaline solution-soluble polymer (P- 3) was obtained. The weight average molecular weight by GPC of the aqueous alkaline solution polymer synthesized in this way is a single sharp curve of 29300 in terms of polystyrene, and is a single composition. The analysis conditions for GPC are described below.
Column: Trade name Shodex 805M / 806M in series manufactured by Showa Denko Co., Ltd. Liquid separation: N-methylpyrrolidone 40 ° C
Flow rate: 1.0 ml / min Detector: Trade name RI-930, manufactured by JASCO Corporation

[Reference Example 6]
<Synthesis of naphthoquinonediazide compound>
In a 1 L separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g of pyridine (0.6 mol) ), And 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added as a powder at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected, and the product was detected as a single peak with a purity of 99%. This reaction solution was dropped as it was into 1 L of ion-exchanged water with stirring, and the precipitate was filtered off, and then 500 ml of THF was added and dissolved by stirring. This homogeneous solution was dissolved in cation exchange resin: Amberlyst 15 (manufactured by Organo). ) Residual pyridine was removed through a glass column packed with 100 g. Next, this solution was dropped into 3 L of ion exchange water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.

The product is imidized, it not characteristic absorption of amide groups in the vicinity of 1540 cm ^-1 and 1650 cm ^-1 appear characteristic absorption of an imide group 1394Cm ^-1 and 1774 cm ^-1 in the IR spectrum is present and, NMR The spectrum was confirmed by the absence of amide and carboxylic acid proton peaks.
Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. . The filtrate obtained at this time was dropped into 5 L of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was dispersed again in 5 L of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like product obtained was vacuum-dried at 40 ° C. for 24 hours to obtain a photosensitive diazoquinone compound (Q-1).

[Reference Example 7]
In a 1 L separable flask, 4,4 ′-(1- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethylidene) bisphenol (trade name: Tris, manufactured by Honshu Chemical Industry Co., Ltd.) as a polyhydroxy compound. -PA) compound 30 g (0.0707 mol) was added, and 47.49 g (0.177 mol) of 1,2-naphthoquinonediazide-4-sulfonic acid chloride in an amount corresponding to 83.3 mol% of the OH group was added to acetone. After putting the solution dissolved by stirring in 300 g, the flask was adjusted to 30 ° C. in a thermostatic bath. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone, charged in a dropping funnel, and then dropped into the flask over 30 minutes. Stirring was continued for another 30 minutes after the completion of dropping, and then hydrochloric acid was added dropwise, followed by further stirring for 30 minutes to complete the reaction. Thereafter, filtration was performed to remove triethylamine hydrochloride. The filtrate obtained here was added dropwise with stirring to a 3 L beaker in which 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred to obtain a precipitate. The precipitate was washed with water and filtered, and then dried under reduced pressure at 40 ° C. for 48 hours to obtain a photoacid generator (Q-2).

[Reference Example 8]
As a reaction container, a glass separable three-necked flask equipped with a Teflon (registered trademark) vertical stirrer was used.
A reaction vessel was charged with 131.0 g of di-t-butyl dicarbonate and 780 g of γ-butyrolactone, and slowly added a solution prepared by mixing 132.8 g of 3-aminopropyltriethoxysilane and 270 g of γ-butyrolactone at room temperature. The solution was added dropwise at room temperature. The reaction solution exothermed to about 40 ° C as it was added dropwise. In addition, the generation of carbon dioxide gas was confirmed with the reaction. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then the reaction solution was confirmed by high performance liquid chromatography (HPLC). As a result, no starting material was detected and the product was detected as a single peak with a purity of 98%. In this way, an adhesion assistant solution was obtained.

<Preparation of photosensitive resin composition>
[Examples 1-13, Comparative Examples 1-14]
Obtained in Reference Examples 6 and 7 with respect to 100 parts by mass of the hydroxy polyamide (P-1, P-2, P-3) obtained in Reference Example 3, Reference Example 4 and Reference Example 5. After dissolving photosensitive diazoquinone compounds (Q-1, Q-2) and unsaturated compounds of the following C-1 to C-10 in 170 to 220 parts by mass of GBL, 30 parts of the adhesion assistant obtained in Reference Example 8 is obtained. In addition, it filtered with a 0.2 micrometer filter, and prepared the photosensitive resin composition of Examples 1-13 shown in the following Table 1, and Comparative Examples 1-14.
(C-1) BANI-M (Maruzen Petrochemical: trade name)
(C-2) BANI-H (Maruzen Petrochemical: trade name)
(C-3) BANI-D (Maruzen Petrochemical: trade name)
(C-4) BANI-X (Maruzen Petrochemical: trade name)
(C-5) tetramethylene pyromellitic acid (C-6) triallyl trimellitic acid (C-7) trimethylolpropane trimethacrylate (C-8) N, N'-1,3-phenylene dimaleimide (C-9) 4,4'-bismaleimide diphenylmethane)
(C-10) Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane

<Evaluation of photosensitive resin composition>
(1) Patterning characteristic evaluation / Prebaked film preparation and film thickness measurement The photosensitive resin compositions of the above examples and comparative examples were spun onto a 6-inch silicon wafer with a spin coater (clean track Mark 8 manufactured by Tokyo Electron Ltd.). The film for application was obtained by pre-baking at 125 ° C. for 180 seconds on a hot plate. The initial film thickness of each composition was adjusted so that the cured resin film thickness was 7 μm when cured at 320 ° C. for 1 hour. The film thickness was measured with a film thickness measuring device (Lambda Ace manufactured by Dainippon Screen Mfg. Co., Ltd.).

-Exposure This coating film was exposed by changing the exposure amount stepwise using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern.

Development Using an alkali developer (AZ300MIF developer manufactured by AZ Electronic Materials Co., Ltd., 2.38 mass% tetramethylammonium hydroxide aqueous solution), the film thickness after development is 85% of the initial film thickness at 23 ° C. The development time was adjusted so as to develop, followed by rinsing with pure water to form a positive relief pattern.

-Preparation of Cure Film Next, the developed film was cured at 320 ° C. for 1 hour using a temperature rising oven (VF200B manufactured by Koyo Thermo Systems Co., Ltd.) to prepare a cure film.

  In Comparative Examples 5 to 8, 12, and 13, foreign matter was observed in the prebaked film.

In addition, the sensitivity of the photosensitive resin composition, the pattern shape at the time of curing, the cured film ratio, the adhesion, and the development residue were evaluated as follows. The results are shown in Table 2 below.
[Sensitivity (mJ / cm ² )]
The minimum exposure amount that can completely dissolve and remove the exposed part of the coating film at the specified post-development film thickness.

[Pattern shape after curing (evaluated by taper angle)]
Using a S-2400 type Hitachi scanning electron microscope manufactured by Hitachi, Ltd., a cross section of the 50 μm line after curing was observed. In this cross section, as shown in FIG. 1, the angle formed by the pattern side surface of the line and the substrate was determined as the taper angle. If the taper angle is 50 ° or more, it can be determined that it is preferable as a surface protective film and an interlayer insulating film of a semiconductor device.

[Cure residual film rate]
(Relief pattern film thickness after curing) / (Relief pattern film thickness after development) × 100

[Adhesion]
Dissolved or peeled dimension (μm) of the developed line & space pattern in a portion exposed at an exposure amount corresponding to twice the minimum exposure amount obtained above.

[Development residue]
Whether an undissolved component (development residue) during development was observed in the exposed portion of the developed film obtained under the above conditions.
A: None (good), B: observed in part, C: observed over the entire surface.

  The photosensitive resin composition of the present invention includes a surface protective film for semiconductor devices, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for devices having a bump structure, and an interlayer insulating film for multilayer circuits It can be suitably used as a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film and the like.

(A) Substrate surface (b) Surface side face of protective film θ Taper angle

Claims (6)

(A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, Y ₁ is a divalent organic group having at least 2 carbon atoms, and m ₁ is 1 It is an integer of ~ 1000. } With respect to 100 parts by mass of the aqueous alkali-soluble polymer having a hydroxyamide structure represented by (B) , 1 to 50 parts by mass of a compound having a naphthoquinonediazide structure , (C) the following general formula (2):

{In the formula, D ₁ has at least one functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an organic group that can be cross-linked, and M ₁ represents —CH ₂ —, A group selected from the group consisting of —O— and —S—, wherein Z ₁ is a divalent organic group, n ₁ is an integer of 1 to 4, and there are a plurality of D ₁ The plurality of D ₁ may be the same or different. A photosensitive resin composition comprising a compound 1 to 40 parts by mass represented by}, (1) a step of a photosensitive resin layer made of the photosensitive resin composition is formed on the substrate, wherein the photosensitive The thickness of the resin film after curing when the photosensitive resin composition is spin-coated and cured at 320 ° C. for 1 hour is set to an initial film thickness of 7 μm. (2) Exposed with actinic radiation through a mask or light, Direct irradiation with electron beam or ion beam, where exposure is performed with a minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film using a stepper having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern to, (3) a step of eluting or removing the exposed portions or irradiated portions, where an alkaline developing solution (2.38 wt% aqueous tetramethylammonium hydroxide solution), the film thickness after development under the condition of 23 ° C. 85% of the initial film thickness The development time is adjusted so as to develop, followed by rinsing with pure water. (4) A step of heat-treating the obtained relief pattern, wherein the temperature is increased by 1 at 320 ° C. using a temperature rising oven. The said photosensitive resin composition characterized by the taper angle of the hardening relief pattern obtained by the manufacturing method of the hardening relief pattern containing time curing becoming 50 degrees or more and 71 degrees or less. (C) The compound represented by the general formula (2) is represented by the following general formula (3):

The photosensitive resin composition of Claim 1 selected from the group which consists of a compound represented by these. (A) An alkaline aqueous solution-soluble polymer having a hydroxyamide structure represented by the general formula (1) is represented by the following general formula (4):

{In the formula, X ₃ represents a single bond and the following general formula (5):

And L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a methyl group, and L ₄ represents a hydrogen atom or a methyl group. or a hydroxyl group, and _{m 1} is an integer of 1 to 1,000. } The photosensitive resin composition of Claim 1 which has a structure represented by these. (A) The terminal of the alkaline aqueous solution-soluble polymer having a hydroxyamide structure represented by the general formula (1) is represented by the following general formula (6):

{Wherein L ₅ represents a group selected from the group consisting of —CH ₂ —, —O—, and —S—, and L ₆ represents a hydrogen atom or an alkyl group. } The photosensitive resin composition of Claim 1 selected from the group consisting of. (1) The process of forming the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-4 on a board | substrate, (2) It exposes with actinic radiation through a mask, or light rays By a method for producing a cured relief pattern, including a step of directly irradiating an electron beam or an ion beam, (3) a step of eluting or removing an exposed portion or an irradiated portion, and (4) a step of heat-treating the obtained relief pattern. The obtained cured relief pattern having a taper angle of 50 ° to 71 °.   A semiconductor device comprising the cured relief pattern according to claim 5.

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